1-naphthaleneacetic acid



Patented July 18, 1939 l-NAPHTHALENEACETIC ACID Richard 0. Dublin, Jr., on Greenwich, and

Ingenium Hechenbleikner, Riverside, Conn., as-

signors to American Cyanamid Company, New

York, N. Y., a corporation of Maine No Drawing. Application June so, 1938,

Serial No. 216,752

3 Claims.

This invention relates to an improved process for the synthesis of l-naphthaleneacetic acid, and

an improved product.

l-naphthaleneacetic acid is one of the plant duction of l-naphthalene-methyl cyanide which.

is then saponifled to produce the lnaphth'aleneacetic acid. It has been proposed to obtain the nitrile by starting from methyl naphthalene by bromina-tion and treatment with potassium cy- -anide. This process produces both poor yields ,"and a product contaminated with impurities -'which are diflicult to remove and which hitherto have never been removed completely. It is an additional feature of the present invention that a new pure l-naphthaleneacetic acid is produced which has "never hitherto been obtained.

According to the present invention, l-naphthylmethyl chloride is prepared from naphthalene, formaldehyde, hydrochloric acid and sulfuric acid, and the crude reaction product without isolation is dissolved in a suitable solvent such as ethanol and treated with sodium cyanide. Hydrolysis is then effected, preferably without separation, and the l-naphthaleneacetic acid is then recrystallized from water yielding a product having a melting point of between 134 and 135 0., whereas the product which has been hitherto known had a melting point of not over s 1 Example A mixture of 256 parts of refined naphthalene,

250 parts by volume of 30% formaldehyde solution and 424 parts by volume of concentrate hydrochloric acid are placed in a kettle equi ped with an efficient stirring device. The temperature is maintained at to C. and 278 parts by volume of concentrated sulfuric acid are introduced gradually during 6 to 7 hours, stirring 5 being vigorous. After all of the sulfuric acid has been added, the mixture is heated at 60 C. for an additional 20 hours.

The mixture is then cooled, and an equal volume of cold water is added. Separation into layers takes place, one being a light colored oil which is separated from the aqueous layer and'washed with water and sodium bicarbonate until'neutral. Approximately 25 0 parts of oil are obtained.

The crude l-naphthylmethyl chloride is dissolved in 250 volumes of ethanol and treated with 72.5 parts of sodium cyanide. The mixture is refluxed for 12 hours on a steam bath. The 1-naphthalene acetonitrile, without isolation, is then treated with parts of sodium hydroxide and the mixture refluxed for an additional 10 hours. The alcohol is then removed by distillation and the residue is dissolved injust suflicient water to effect solution which is slightly dark colored. The solution is then extracted with ether and the water layer separated and heated for a short time to drive off any solvent remaining. The warm water layer which is a solution of'the sodium salt of l-naphthaleneacetic acid is then treated with 425 volumes of 25% sulfuric acid followed by cooling. The l-naphthaleneacetic acid separates out and is filtered with, suction. The yield is 235 parts or 70% based on the original naphthalene.

The crude product has a melting point of C. After one recrystallization from water, the melting point is C. and after a second, 134 to 135 C.

Instead of using ether for extracting impurities from the water solution, a hydrocarbon solvent such as petroleum ether may be used.

What we claim is:

1. A process of producing l-naphthaleneacetic acid which comprises reacting naphthalene with formaldehyde, hydrochloric acid and sulfuric acid to produce l-naphthlymethylchloride, separating the crude l-naphthylmethyl chloride, from unreacted acid, dissolving the crude l-naphthylmethyl chloride in an organic solvent, heating it with an alkali metal cyanide, adding caustic alkali to the reaction mixture and heating until hydrolysis has taken place, removing the organic solvent by distillation, acidifying and sep' arating out the l-naphthaleneacetic acid.

2. A process of producing l-naphthaleneacetic acid which comprises reacting at 60 to 70 C.

naphthalene with formaldehyde, hydrochloric I ing the crude i-naphthylmethyl chloride in 95%:

ethanol, heating it: with :sodium cyanide, lddinr caustic alkali to the 1 reaction. mixture and. heating. untllhydrolysls' has taken place, removing the ethanol by'distillatlon, acidifying and separating outithe .l-naphthaleneaceticacid;

3; A process-of producing I-naphthaleneacetic acidwhich: comprises reacting at 60 mime C." naphthalenewlthformaldehyde,hydrochloric acid and sulfuric acid to 'produce l-naphthylmethyl' chloride; separating the crude l-naphthylmethyl chlorides-from unreacted acid, dissolving-them:

l -ncphthylmethylichlorideinflb9t ethonol, heatit; with, sodium'vcyanide, adding caustic a1- to the reaction mixture and heating until hydrolysis' h'asl taken place, 7 removing: the alcohol 

